Electrochromic band-shifts have been investigated in Photosystem II (PSII) from Thermosynechoccocus elongatus. Firstly, by using Mn-depleted PsbA1-PSII and PsbA3-PSII in which the QX absorption of PheD1 differs, a band-shift in the QX region of PheD2 centered at ~ 544 nm has been identified upon the oxidation, at pH 8.6, of TyrD. In contrast, a band-shift due to the formation of either QA•- or TyrZ• is observed in PsbA3-PSII at ~ 546 nm, as expected with E130 H-bonded to PheD1 and at ~ 544 nm as expected with Q130 H-bonded to PheD1. Secondly, electrochromic band-shifts in the Chla Soret region have been measured in O2-evolving PSII in PsbA3-PSII, in the PsbA3/H198Q mutant in which the Soret band of PD1 is blue shifted and in the PsbA3/T179H mutant. Upon TyrZ•QA•- formation the Soret band of PD1 is red shifted and the Soret band of ChlD1 is blue shifted. In contrast, only PD1 undergoes a detectable S-state dependent electrochromism. Thirdly, the time resolved S-state dependent electrochromism attributed to PD1 is biphasic for all the S-state transitions except for S1 to S2, and shows that: i) the proton release in S0 to S1 occurs after the electron transfer and ii) the proton release and the electron transfer kinetics in S2 to S3, in T. elongatus, are significantly faster than often considered. The nature of S2TyrZ• is discussed in view of the models in the literature involving intermediate states in the S2 to S3 transition.
Keywords: Electrochromism; Oxygen evolution; Photosystem II; Proton release; S-state transition kinetics.
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